Photopolymerizable resin compositions and use thereof

ABSTRACT

This invention relates to a photopolymerizable resin composition containing resin component (A) composed of a resin and/or a resin-forming ingredient and a photopolymerization initiator (B) wherein the component (A) comprises an addition-polymerizable compound (A1) having at least two ethylenically unsaturated groups and the photopolymerization initiator (B) comprises a diaminobenzophenone compound (B1), an N-phenylglycine compound (B2), and at least one kind of compound selected from a group of a 3,3′,4,4′-tetra(alkylperoxycarbonyl)benzophenone (B3), 2-methyl-1-[4-(thiomethyl)phenyl]- 2-morpholinopropan-1-one (B4), and a 1,3,5-triazine derivative (B5) containing at least one trihalomethyl group as substituent. A photopolymerizable resin composition of this invention excels in resolution, adhesion of patterns, development latitude, and curing on the surface and inside and can be used advantageously in insulating films, colored films, inks for color filters, resists for semiconductors, and insulating spacers for touch panels.

This application is the national phase under 35 U.S.C. § 371 of PCTInternational Application No. PCT/JP99/03060 which has an Internationalfiling date of Jun. 8, 1999, which designated the United States ofAmerica.

FIELD OF TECHNOLOGY

This invention relates to photopolymerizable resin compositions whichare useful for applications such as insulating films for semiconductors,resists for semiconductors, protective films for color filters, coloredfilms, and insulating spacers for touch panels.

BACKGROUND TECHNOLOGY

Photopolymerizable resin compositions are exposed to light, generallywith the use of UV as light source, in their applications toletterpress, relief images, photoresists, and the like and the resincompositions of this type contain a resin component which constitutesthe main body of an image to be formed and a photopolymerizationinitiator which, upon exposure to light such as UV, generates an activespecies for polymerization.

From the standpoint of environmental problems and ease of obtaining alarge difference in solubility before and after exposure to light inrecent years, there is a preference for an aqueous solution of alkali toan organic solvent in the development step in the application ofphotopolymerizable resin compositions. In such a case, a combination ofan addition-polymerizable compound containing an ethylenicallyunsaturated group and a resin soluble in an aqueous solution of alkaliis used preferentially for the resin component which constitutes themain body of an image. There is a demand for higher sensitivity for thistype of photopolymerizable resin compositions and numerous studies arein progress on photopolymerization initiators in order to enhance thesensitivity.

Many substances are known already for photopolymerization initiators;for example, benzoin and its derivatives and substituted andunsubstituted quinones [Photopolymer Handbook, Chapter 6, edited byPhotopolymer Konwakai (in Japanese)]. These compounds, however, are notsufficiently sensitive to the i-line (365 nm), h-line (405 nm) andg-line (437 nm) mainly emitted by a commonly used mercury vapor lamp.

A combination of benzophenone, a diaminobenzophenone compound, and anN-phenylglycine compound has been proposed for use as aphotopolymerization initiator in order to obtain photopolymerizableresin compositions with enhanced sensitivity in the range 300-450 nm[Japan Tokkyo Koho Hei 4-27541 (1992)].

However, when a photopolymerizable resin composition containing thiscombination of benzophenone, a diaminobenzophenone compound, and anN-phenylglycine compound is exposed to light whose main component is thei-line, the composition lacks sufficient sensitivity to undergo curingon the surface when the film thickness is less than 10 μm duringexposure to light. On the other hand, when the film thickness exceeds 10μm during exposure to light, the addition of the diaminobenzophenonecompound is diminished in order to advance the photocuring in the insideuntil the adherence of a pattern during development is secured; then thegeneration of radicals from the photopolymerization initiatordiminishes, which leads to the hindrance of the surface curing androughening of the surface of the film after development.

Methods for incorporating a halomethyltriazine as photopolymerizationinitiator into colored photopolymerizable compositions for use in colorfilters are known [Japan Tokkyo Koho Sho 59-28328 (1984), Japan TokkyoKoho Hei 5-88243 (1993), Japan Kokai Tokkyo Koho Hei 6-167808 (1994),and Japan Kokai Tokkyo Koho Hei 6-27662 (1994)].

The aforementioned photopolymerizable compositions containing ahalomethyltriazine are colored yellow, although highly sensitive, andposed a problem of reducing the transmission of blue filters inparticular and the compound in question was a cause of extensivediscoloration during heating.

There is a demand for displays with high color purity and brightness forcolor liquid crystal displays in recent years. In the case of colorfilters with high color purity, light in the ultraviolet region reachesthe deep part of the film with difficulty and this poses problems suchas poor adhesion of a pattern due to insufficient curing in the deeppart of the film and peeling off of a pattern during development.Moreover, absorption of the photopolymerization initiator and yellowingafter heat treatment sometimes diminished the brightness of colorfilters.

Accordingly, an object of this invention is to provide aphotopolymerizable resin composition which excels in resolution,development latitude and surface curability and shows enhancedsensitivity particularly to the i-line and, furthermore, to provide aphotopolymerizable resin composition which is curable even at a filmthickness of, say, 10 μm or more and, when used in a coloredpolymerizable composition, is highly transparent and does notsignificantly affect the color characteristics. Another object of thisinvention is to provide a photopolymerizable resin composition which ishighly sensitive to UV, not only to the i-line but also to lines in therange to the g-line.

A further object of this invention is to provide a blue ink withexcellent color characteristics. A still further object of thisinvention is to provide a film to be obtained by applying theaforementioned photopolymerizable resin composition or a blue inkfollowed by curing and to provide a color filter containing said film asblue filter or protective film.

DISCLOSURE OF THE INVENTION

Thus, this invention relates to a photopolymerizable resin compositioncomprising a resin and/or a resin-forming ingredient as component (A)and a photopolymerization initiator (B), wherein the component (A)comprises an addition-polymerizable compound (A1) which shows a boilingpoint of 100° C. or higher at normal pressure and has at least 2ethylenically unsaturated groups in the molecule and the component (B)comprises a diaminobenzophenone compound (B1) represented by thefollowing general formula (1)

(in which R is a hydrogen atom or an alkyl group with 1-3 carbon atoms,either identical with or different from each other), an N-phenylglycinecompound (B2) represented by the following general formula (2)

(in which R is an alkyl group with 1-8 carbon atoms, R′ is a hydrogenatom or an alkyl group with 1-8 carbon atoms, n is an integer in therange 0-5, and R may be identical with or different from each other whenn is 2 or more), and at least one kind of compound selected from a groupof a 3,3′,4,4′-tetra(alkylperoxycarbonyl)benzophenone (B3) representedby the following general formula (3)

(in which R is an alkyl group with 1-8 carbon atoms, identical with ordifferent from each other),2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (B4), and a1,3,5-triazine derivative (B5) containing at least one trihalomethylgroup as substituent.

This invention also relates to the aforementioned photopolymerizableresin composition wherein the component (A) composed of a resin and/or aresin-forming ingredient comprises the addition-polymerizable compound(A1) and an alkali-soluble resin (A2) and the ratio (A1)/(A2) by weightis 10/90-90/10.

This invention further relates to the aforementioned photopolymerizableresin composition which comprises 100 parts by weight of the component(A), 0.05-2.0 parts by weight of a diaminobenzophenone compound (B1),0.2-2 parts by weight of an N-phenylglycine compound (B2), 0-2.5 partsby weight of a 3,3′,4,4′-tetra(alkylperoxycarbonyl)benzophenone (B3),0-5 parts by weight of2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (B4), and 0-1part by weight of a 1,3,5-triazine derivative (B5). Likewise, thisinvention relates to the aforementioned photopolymerizable resincomposition which comprises 100 parts by weight of the component (A),0.05-2.0 parts by weight of a diaminobenzophenone compound (B1), 0.2-2parts by weight of an N-phenylglycine compound (B2), 0.1-2.5 parts byweight of a 3,3′,4,4′-tetra(alkylperoxycarbonyl)benzophenone (B3), 1-5parts by weight of2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (B4), and0-0.5 part by weight of a 1,3,5-triazine derivative (B5). Still more,this invention relates to the aforementioned photopolymerizable resincomposition wherein the component (A) comprises theaddition-polymerizable compound (A1) and the alkali-soluble resin (A2)at the ratio (A1)/(A2) by weight of 10/90-90/10 and the compositioncomprises 100 parts by weight of the sum of (A1) and (A2), 0.05-2.0parts by weight of a diaminobenzophenone compound (B1), 0.2-2 parts byweight of an N-phenylglycine compound (B2), 0-2.5 parts by weight of a3,3′,4,4′-tetra(alkylperoxycarbonyl)benzophenone (B3), 1-5 parts byweight of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one(B4), and 0-0.5 part by weight of a 1,3,5-triazine derivative (B5).

In addition, this invention relates to the aforementionedphotopolymerizable resin composition into which a blue colorant isincorporated and to a blue ink. This invention relates to a filmobtained by applying the photopolymerizable resin composition or blueink followed by curing. This invention also relates to a color filtercontaining the aforementioned film.

A photopolymerizable resin composition of this invention contains thecomponent (A) composed of a resin and/or a resin-forming ingredient andthe photopolymerization initiator (B) as essential ingredients. As thecomponent A comprises a resin and/or a resin-forming ingredient, thatis, a resin and/or a compound polymerizable into resin, the component Aas a whole is bound to exist as resin after polymerization. For thisreason, the component A will be hereinafter referred to as resincomponent (A).

The addition-polymerizable compound (A1), an essential ingredient of theresin component (A), reacts with radicals generated by thephotopolymerization initiator upon exposure to ultraviolet light,undergoes polymerization, crosslinking, and curing, and gives strengthand hardness to the film after exposure. When coexisting with thealkali-soluble resin (A2), the compound (A1) becomes involved in alkaliinsolubilization of the exposed portion.

The addition-polymerizable compound (A1) may be any of those compoundswhich boil at 100° C. or higher at normal pressure and contain at least2 ethylenically unsaturated groups in the molecule and such compoundsinclude esters resulting from the reaction of polyhydric alcohols withα, β-unsaturated carboxylic acids such as diethylene glycoldi(meth)acrylate [(meth)acrylate means acrylate or methacrylatehereinafter], triethylene glycol di(meth)acrylate, tetraethylene glycoldi(meth)acrylate, trimethylolpropane di(meth)acrylate,trimethylolpropane tri(meth)acrylate, 1,3-propanediol (meth)acrylate,1,3-butanediol (meth)acrylate, pentaerythritol tetra(meth)acrylate,dipentaerythritol hexa(meth)acrylate,2,2-bis(4-acryloyloxydiethoxyphenyl)propane,2,2-bis(4-methacryloyloxypentaethoxyphenyl)propane, and a mixture of2,2-bis(4-methacryloyloxypolyethoxyphenyl)propanes (BEP-500, tradenameof Shin-Nakamura Chemical Co., Ltd.), compounds obtained by the additionof glycidyl group-containing compounds with α, β-unsaturated carboxylicacids such as trimethylolpropane triglycidyl ether tri(meth)acrylate,bisphenol A diglycidyl ether di(meth)acrylate, and fluorenebisphenoldiglycidyl ether di(meth)acrylate (ASF400, tradename of Nippon SteelChemical Co., Ltd.), unsaturated amides such as methylenebisacrylamideand 1,6-hexamethylenebisacrylamide, and vinyl esters such as divinylsuccinate, divinyl adipate, divinyl phthalate, divinyl terephthalate,and divinyl benzene -1,3-disulfonate.

The addition-polymerizable compound (A1) may be either alow-molecular-weight compound or a high-molecular-weight compound, butit is preferably a low-molecular-weight compound with a molecular weightof 1,000 or less from the standpoint of good solvent solubility and lowviscosity.

Incorporation of the alkali-soluble resin (A2) as one of the resincomponents gives a resin composition of a good alkali developmentquality. Desirable as the alkali-soluble compound (A2) are those whichcontain acidic groups such as carboxylic and phenolic hydroxyl groups inthe molecule and they may contain ethylenically unsaturated groups atterminal locations. Examples of the alkali-soluble resin (A2) arecopolymers of (meth)acrylic acid and alkyl (meth)acrylate and copolymersof (meth)acrylic acid, alkyl (meth)acrylate and vinyl monomerscopolymerizable with the foregoing two (meth)acrylic compounds. Alkyl(meth)acrylates here include butyl (meth)acrylate and 2-ethylhexyl(meth)acrylate. Vinyl monomers copolymerizable with (meth)acrylic acidand alkyl (meth)acrylate include tetrahydrofurfuryl (meth)acrylate,glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate,2,2,3,3-tetrafluoropropyl (meth)acrylate, acrylamide, diacetoneacrylamide, styrene, and vinyltoluene.

Additional examples of the alkali-soluble resin (A2) are ester oligomerscontaining carboxyl groups such as partial esters of styrene-maleicanhydride copolymers, partial esters of the copolymers of a diol and anacid dianhydride, and partial esters of unsaturated polyesters.

Recommended for use as the alkali-soluble resin (A2) is a compound whichcontains alkali-developable acidic functional groups such as carboxyland phenolic hydroxyl groups and, moreover, occurs either as a solidwith a molecular weight of 600 or more or a polymer with a numberaverage molecular weight of 1,000 or more in order to render the filmfree from cracking and tackiness after application and drying of theresin composition.

Furthermore, a compound containing both two or more ethylenicallyunsaturated groups and alkali-solubilizing carboxyl groups in themolecule may be used as alkali-soluble resin (A2) together with theaddition-polymerizable compound (A1). Such simultaneous use desirablyprovides a photopolymerizable composition with good resolution. The casein point is an addition product of an acid anhydride with a compoundcontaining a hydroxyl group and two or more ethylenically unsaturatedgroups. For example, addition products of an acid with bisphenol epoxy(meth)acrylate described in Japan Kokai Tokkyo Koho Hei 6-1938 (1994)are desirable as such. In the cases where the film shows no crackingafter drying and the tackiness presents no problem, for example, whenexposure is effected in proximity mode while avoiding exposure incontact mode, the alkali-soluble resin (A2) is not necessarily a resinand may be a compound capable of polymerizing into resin.

In case the addition-polymerizable compound (A1) and the alkali-solubleresin (A2) are used together, the ratio (A1)/(A2) by weight is10/90-90/10, preferably 20/80-80/20. Where the proportion of thealkali-soluble resin (A2) is lower than what this ratio stipulates, thephotocured product becomes brittle and the solubility in an alkalinedeveloper decreases because of a low acid value of the unexposed portionof the resin composition. On the other hand, where the proportion of thealkali-soluble resin (A2) is higher, the addition-polymerizable compound(A1) does not function sufficiently to form a crosslinked structure andbring about alkali insolubilization in the exposed portion and, besides,the acid value increases to such an extent as to cause an increase inthe solubility in an alkaline developer not only in the unexposedportion but also in the exposed portion.

In addition to the aforementioned (A1) and (A2), it is allowable to add,as other ingredients of the resin component (A), reactive diluents thatare miscible with (A1) and (A2) and contain only one ethylenicallyunsaturated group in the molecule or resin ingredients that are neitherphotopolymerizable nor alkali-soluble, for example, epoxy resins, rosinresins, and alkyd resins, in proportions less than 50% by weight of theresin component (A) as a whole. When the addition is 50% by weight ormore, the extra components cause such defects as decrease in solubilitydue to a drop of the acid value in the unexposed portion and loss ofpatterns during development due to a drop of crosslinking density in theexposed portion.

The photopolymerization initiator (B) to be used in photopolymerizablecompositions of this invention generates radicals upon exposure tolight, particularly to UV, and initiates the polymerization of theaddition-polymerizable compound (A1). The photopolymerization initiator(B) to be used in photopolymerizable resin compositions of thisinvention comprises (B1) and (B2) as essential ingredients andadditionally at least one kind of compound selected from (B3), (B4), and(B5).

The photopolymerization initiator (B1) is a diaminobenzophenone compoundrepresented by the aforementioned general formula (1). In the generalformula (1), R is a hydrogen atom or an alkyl group with 1-3 carbonatoms and, although R may be identical with or different from oneanother, it is preferably methyl or ethyl group. Typical examples of(B1) are 4,4′, -diethylaminobenzophenone and4,4′-dimethylaminobenzophenone.

The photopolymerization initiator (B2) is an N-phenylglycine compoundrepresented by the aforementioned general formula (2). In the generalformula (2), R is an alkyl group with 1-8 carbon atoms, R′ is a hydrogenatom or an alkyl group with 1-8 carbon atoms, n is an integer in therange 0-5, and R may be identical with or different from one anotherwhen n is 2 or more. Preferably, R is methyl or ethyl group, R′ is ahydrogen atom or an alkyl group with 1-4 carbon atoms and n is 0 or 1.Examples of (B2) are N-phenylglycine, N-phenylglycine ethyl ester,N-phenylglycine methyl ester, N-phenylglycine butyl ester, andN-phenylglycine propyl ester.

The photopolymerization initiator (B3) is a3,3′,4,4′-tetra(alkylperoxycarbonyl)benzophenone represented by theaforementioned general formula (3). In the general formula (3), R is analkyl group with 1-8 carbon atoms and is either identical with ordifferent from one another. Preferably, R is a branched alkyl group. Atypical example of (B3) is3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone.

The photopolymerization initiator (B4) is2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one. Thiscompound is available, for example, as Irgacure 907 (tradename of CibaSpeciality Chemical).

The photopolymerization initiator (B5) is a 1,3,5-triazine derivativecontaining at least one trihalomethyl group as substituent. The1,3,5-triazine derivative (B5) needs to be 1,3,5-triazine substitutedwith at least one trihalomethyl group on a carbon atom in the ring. Theother two carbon atoms in the ring may or may not contain a substituent;when a substituent is present, it may be a trihalomethyl group, an alkylgroup with 1-18 carbon atoms, a substituted alkyl group, an alkylenegroup, a substituted alkylene group, an aryl group, or a substitutedaryl group. The halogen in a trihalomethyl group may be chlorine orbromine. Examples of (B5) are2,4,6-tris(trichloromethyl)-1,3,5-triazine,2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine,2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine,2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine.

These photopolymerization initiators are incorporated into 100 parts byweight of the resin component (A) as follows: diaminobenzophenonecompound-(B1), 0.05-2.0 parts by weight, preferably 0.08-1.0 part byweight; N-phenylglycine compound (B2), 0.2-2 parts by weight, preferably0.3-1.5 parts by weight;3,3′,4,4′-tetra(alkylperoxycarbonyl)benzophenone (B3), 0-2.5 parts byweight, preferably 0.1-2.5 parts by weight, more preferably 0.5-2.0parts by weight;2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (B4), 0-5parts by weight, preferably 1-5 parts by weight, more preferably 2-4parts by weight; and 1,3,5-triazine derivative (B5), 0-1 part by weight,preferably 0 or 0.1-0.7 part by weight, more preferably 0 or 0.2-0.5part by weight. The proportion of diaminobenzophenone compound (B1) ispreferably controlled at 0.05-1 part by weight when the film thicknessis 10 μm or more and at 0.5-2 parts by weight when the film thickness isless than 10 μm while that of 1,3,5-triazine derivative (B5) iscontrolled at 0-0.5 part by weight when the film thickness is 30 μm ormore or the composition is for blue ink.

A further advantage can be gained by incorporating thephotopolymerization initiators into 100 parts by weight of the resincomponent (A) in the following proportions: diaminobenzophenone compound(B1), 0.05-2.0 parts by weight; N-phenylglycine compound (B2), 0.2-2parts by weight; 3,3′,4,4′-tetra(alkylperoxycarbonyl)benzophenone (B3),0.1-2.5 parts by weight;2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (B4), 1-5parts by weight, and 1,3,5-triazine derivative (B5), 0-0.5 part byweight.

In the cases where the resin component (A) is mainly composed of theaddition-polymerizable compound (A1) and the alkali-soluble resin (A2),that is, where (A1) and (A2) account for the greater part of (A), theexpression “100 parts by weight of the resin component (A)” can bereplaced by “100 parts by weight of the sum of (A1) and (A2).”

It is recommended to incorporate the photopolymerization initiators into100 parts by weight of the sum of (A1) and (A2) in the followingproportions: diaminobenzophenone compound (B1), 0.05-2.0 parts byweight, preferably 0.08-1.0 part by weight; N-phenylglycine compound(B2), 0.2-2 parts by weight, preferably 0.3-1.5 parts by weight;3,3′,4,4′-tetra(alkylperoxycarbonyl)benzophenone (B3), 0-2.5 parts byweight, preferably 0.1-2.5 parts by weight, more preferably 0.5-2.0parts by weight;2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (B4), 0-5parts by weight, preferably 1-5 parts by weight, more preferably 2-4parts by weight; and 1,3,5-triazine derivative (B5), 0-1 part by weight,preferably 0 or 0.1-0.7 part by weight, more preferably 0 or 0.2-0.5part by weight.

When the proportion of diaminobenzophenone compound (B1) is short of theaforementioned range, the generation of radicals is insufficient and thesurface curing becomes incomplete due to inhibition by oxygen andsatisfactory properties are not obtained. Conversely, an excessproportion of (B1) causes the absorption of light to occur on thesurface alone during exposure and photocuring of the inside becomesinsufficient. As for the proportion of N-phenylglycine compound (B2), ashortage does not enhance the photosensitivity sufficiently while anexcess lowers the storage stability of photopolymerizable resincompositions.

In the co-presence of (B1) and (B2),3,3′,4,4′-tetra(alkylperoxycarbonyl)benzophenone (B3),2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (B4), and1,3,5-triazine derivative (B5) enhance the sensitivity and, inparticular, promote the surface curing. In addition to enhancement ofthe sensitivity and promotion of the surface curing, (B3) is effectivefor enhancing the sensitivity, particularly not only to the i-line butalso to the g-line and the h-line. The proportion of (B3), when in use,must be 0.1 part by weight or more per 100 parts by weight of the resincomponent (A) to enhance the sensitivity sufficiently. An excess of(B3), however, lowers the storage stability. When used in combinationwith the aforementioned (B1) and (B2), (B4) markedly enhances thephotosensitivity. Sufficient enhancement is not obtained unless (B4) isused in a proportion of 1 part by weight or more per 100 parts by weightof the resin component (A). Although 1,3,5-triazine derivative (B5) iseffective for enhancing the sensitivity and promoting the surfacecuring, an excess of it causes insufficient curing inside the film orloss of patters and also hinders the transmission of blue light.Therefore, it is recommended to control the proportion of (B5) at 1 partby weight or less, preferably 0.5 part by weight or less, per 100 partsby weight of the resin component (A).

These photopolymerization initiators are used desirably in the followingcombinations:

{circle around (1)} (B1)-(B2)-(B3)-(B4)-(B5)

{circle around (2)} (B1)-(B2)-(B3)-(B4)

{circle around (3)} (B1)-(B2)-(B3)

{circle around (4)} (B1)-(B2)-(B4)

In particular, in the case of the preparation of blue inks where thetransmission of the i-line needed for curing diminishes, it isadvantageous to use the combination of {circle around (1)}, {circlearound (2)} or {circle around (3)} containing (B1), (B2), and (B3) whichare capable of enhancing sensitivity even to the g-line to effectsufficient curing of the inside. The combination {circle around (1)},{circle around (2)} or {circle around (3)} which contains (B4) or (B5)is advantageous for raising the surface hardness. However, (B5) absorbsa part of blue light as mentioned above, and it needs to be used in arestricted amount. Therefore, an alternative is to use (B3) or (B4) as awhole or partial substitute for (B5).

In formulating photopolymerizable resin compositions of this invention,it is necessary to exercise special care in determining the amount ofthe photopolymerization initiator (B) to be incorporated into the resincomponent (A) because a shortage of (B) causes insufficient photocuringwith the resultant thinning of the lines and roughening of the surfaceduring development while an excess of (B) causes the majority of lightto be absorbed in the upper portion of the film leaving the lowerportion of the film uncured.

In the cases where a photopolymerizable resin composition of thisinvention is applied in a relatively thick layer and cured, special caremust be given to the amount of photopolymerization initiator to beadded. With addition of an excessive amount, the absorption of lightoccurs mostly in the upper portion with little light reaching the lowerportion and the lower portion remains uncured. On the other hand, withaddition of a too small amount, the curing occurs insufficiently andthinning of the lines and overdevelopment occur. One of the methods todetermine the optimal composition of additives is to apply aphotopolymerizable resin composition, expose the film of the appliedcomposition to light, and choose such an amount of additives as to givea transmission of 5-80% at the main wavelength of the light in use. Forexample, in case the curing is effected by the i-line, it is desirableto add the photopolymerization initiators so that the transmission at365 nm becomes 50-80% at a film thickness of 10 μm or exceeds 5% at afilm thickness of 40 μm.

In formulating photopolymerizable resin compositions of this invention,it is allowable to use other known photopolymerization initiators whosemaximum absorption wavelngth lies in the region shorter than the i-line(365 nm) in addition to the aforementioned photopolymerizationinitiators (B1) to (B5). An example of photopolymerization initiators tobe used for this purpose is benzophenone. However, if such apolymerization initiator is added in excess of the amount which reducesthe transmission of the light for exposure at its main wavelenght to 5%or less, it would undesirably cause insufficient curing in the inside.Therefore, the polymerization initiator in question is never used inexcess of 3 parts by weight per 100 parts by weight of the resincomponent (A).

In addition to the resin components and photopolymerization initiators,colorants such as dyes and pigments may be incorporated intophotopolymerizable resin compositions of this invention. A variety ofcolorants are useful for colorants, for example, titania, carbon black,iron oxide, quinacridone pigments, phthalocyanine pigments, azopigments, and acid dyes. Preferable among them are blue dyes or pigmentssuch as phthalocyanine blue.

Where the application involves the color filters for liquid crystaldisplays and liquid crystal projectors, organic pigments are used onaccount of their transparency and color purity. The following aredesirable examples of such organic pigments: for blue, phthalocyaninepigments and indanthrene pigments, particularly ε-phthalocyanine blue(C.I. Pigment Blue 15:6); for red, anthraquinone pigments, quinacridonepigments, diketopyrrolopyrrole pigments, perylene pigments, andparticularly diketopyrrolopyrrole red (C.I. Pigment Red 254) anddianthraquinonyl red (C.I. Pigment Red 177); for green, chlorinatedphthalocyanine green (C.I. Pigment Green 7) and brominatedphthalocyanine green (C.I. Pigment Green 36); for violet, DioxazineViolet (C.I. Pigment Violet 23); for yellow, isoindoline yellow (C.I.Pigment Yellow 83) and Diarylide Yellow (C.I. Pigment Yellow 83). Thesepigments are micro-dispersed in an organic solvent to an averageparticle diameter of 0.2 μm or less in a sand mill together with thosepigment derivatives and graft polymers which contribute to stabilize themicrodispersion and then mixed with photopolymerizable resincompositions to give colored photopolymerizable resin compositions orinks of this invention.

Additives such as the following may also be incorporated intophotopolymerizable resin compositions of this invention: surfactants forimproving levelling during application and reducing uneven evaporationduring drying, coupling agents for improving adhesion to the base plate,fillers for improving the crack resistance during the heat cycle test,and adhesion promoters for facilitating adhesion to fillers.

Moreover, in order to prepare photopolymerizable resin compositions ofthis invention as homogeneous solutions, solvents which are capable ofdissolving the aforementioned components may be incorporated into thecompositions. Such solvents include, for example, a variety of glycolethers such as ethylene glycol monobutyl ether, ethylene glycolmonohexyl ether, ethylene glycol monophenyl ether, propylene glycolmonomethyl ether, propylene glycol monophenyl ether, diethylene glycoldimethyl ether, and triethylene glycol dimethyl ether, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone,isophorone, pentoquinone, N-methylpyrrolidone, and γ-butyrolactone,ethers such as butyl ether, dioxane, and tetrahydrofuran, alcohols suchas methoxybutanol, diacetone alcohol, butanol, and isopropanol,hydrocarbons such as toluene, xylene, and hexane, and esters such asethyl acetate, butyl acetate, and ethyl benzoate.

Colorant-containing photopolymerizable resin compositions of thisinvention can be used as inks. In particular, those containing bluecolorants give excellent blue inks. In applications of the conventionalblue inks composed of photopolymerizable resin composition containingblue colorants, the blue colorants often hinder the photocuring of theinks. With blue inks of this invention, the photocuring proceeds intothe depth because of high sensitivity to a relatively wide wavelengthrange of UV.

Photopolymerizable resin compositions of this invention are available intwo kinds, one composed of the resin component (A) and thephotopolymerization initiator (B) only and the other composed of (A),(B) and other additives and solvents, and they are used differentiallydepending upon the end use. For example, compositions in solution andinks are used in insulating films for semiconductors, resist materialsfor semiconductors, liquid crystal displays, color filter materials forCCD cameras, colored films, touch panels, and insulating spacers fordisplays and they are also used as pattern-forming materials andimage-forming materials.

Regarding the method of use, the one in general practice is to apply aphotopolymerizable resin composition prepared as solution to the base toa given thickness, dry, and expose to active light (UV) of a givenwavelength range to effect photocuring, although not restricted to thisparticular one. The thickness of the applied composition is 0.2-100 μm,preferably 1-3 μm, under a dry condition. The source of active light ispreferably the one which emits mainly the i-, g-, and h-lines. As fordevelopment, it is preferable to dissolve and remove the unexposedportion by alkali development with the use of an aqueous solution ofalkali. There may be a case, as needed, where the whole surface isexposed and the development is omitted.

The application of a photopolymerizable resin composition of thisinvention as color filter is described as an example. Aphotopolymerizable resin composition of this invention, preferablycontaining a suitable solvent and additives, is made into a homogeneoussolution or an ink. The solution or ink is applied to the base plate ofa color filter to a given thickness by such means as spin coating, barcoating, spray coating, or printing coating and dried to form a filmwith a thickness of 0.2-100 μm. The film is exposed through a photomaskto a light source such as super high-pressure mercury lamp,high-pressure mercury lamp, metal halide lamp, far ultraviolet lamp, andvisible light laser and cured. The exposed film is then developed bydissolving the uncured portion in a stream or shower of an aqueoussolution of alkali or an organic solvent, typical alkali being an alkalimetal carbonate such as lithium carbonate, an alkali metal hydroxidesuch as sodium hydroxide, and an organic base such astetramethylammonium hydroxide, and washing with water. In the case of anink, the procedure is repeated for each color. A photopolymerizableresin composition containing no colorant is used as a protective filmfor color filter and it is applied to the base plate for color filter onwhich the ink has been developed, and then similarly dried, exposed, anddeveloped.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the cross section of the film with a thickness of 40μm formed with the use of the photopolymerizable resin composition ofExample 2.

FIG. 2 illustrates the cross section of the film with a thickness of 40μm formed with the use of the photopolymerizable resin composition ofComparative Example 1.

PREFERRED EMBODIMENTS OF THE INVENTION Examples 1-3

Thirty (30) parts by weight of dipentaerythritol hexaacrylate (DPHA) wasused as (A1) and 124 parts by weight of a 56.5 wt % propylene glycolmonomethyl ether acetate solution (70 parts by weight as solid) offluorenebisphenol type epoxy acrylate/acid anhydride addition polymer(V259ME, tradename of Nippon Steel Chemical Co., Ltd.) was used as (A2).

To 100 parts by weight of the sum of (A1) and (A2) were added 15 partsby weight of epoxy resin (XY4000H, tradename of Yuka Shell Epoxy K.K.)for providing alkali resistance after heat treatment, 1.2 parts byweight of a silane coupling agent (S510, tradename of ChissoCorporation) for providing adhesion to the base plate, and 61 parts byweight of propylene glycol methyl ether acetate as solvent.

Then, to 100 parts by weight of the sum of (A1) and (A2) were added2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (Irgacure907, tradename of Ciba) as photopolymerization initiator (B4),4,4′-diethylaminobenzophenone (EABF, tradename of Hodogaya Chemical Co.,Ltd.) as (B1), and N-phenylglycine as (B2) in the amounts shown in Table1 to prepare a photopolymerizable resin composition as a homogeneoussolution.

The photopolymerizable resin composition thus prepared was applied by aspin coater to a glass base plate to a thickness of 10 μm or 40 μm afterdrying and prebaked at 80° C. for 5 minutes when the film thickness was10 μm or at 100° C. for 15 minutes when the film thickness was 40 μm toform a film for interlayer insulating film on the glass base plate.

The film thus formed was exposed through a negative mask to UV(illuminance 1 lmw/cm², i-line as standard) in a light exposureapparatus (HTE505S, tradename of HI-TECK. Co., Ltd.), developed by a 0.7wt % aqueous solution of diethanolamine (28° C.) when the film thicknesswas 10 μm or by a 1.4 wt % aqueous solution of diethanolamine when thefilm thickness was 40 μm and tested for the sensitivity by the followingprocedure.

With the aid of a wedge filter for sensitivity measurement (availablefrom Matsuzaki Shinku K.K.), the specimen was exposed to ultravioletlight at 200 mJ/cm² with i-line as standard in the aforementioned lightexposure apparatus and then developed by a diethanolamine developer, inthe same manner as above, for 60 seconds when the film thickness was 10μm or for 90 seconds when the film thickness was 40 μm. The sensitivitywas determined as the minimum light exposure to give a residual filmafter development. This means the smaller the minimum light exposrue,the higher the sensitivity. The results are shown in Table 1.

Comparative Examples 1-4

The experiment was carried out as in Example 1 except using the kind andamount of photopolymerization initiator shown in Table 1. The resultsare shown in Table 1. The term overdevelopment in Table 1 means thecomplete absence of a residual film after development.

TABLE 1 Photopolymerization initiator Sensitivity (mj/cm²) (part byweight) Film Film Irga- N- thick- thick- cure Benzo- Phenyl- ness ness907 phenone EABF glycine 10 μm 40 μm Example 1 3.0 0 0.1 0.4  90  85Example 2 3.0 0 0.1 1.0  85  65 Example 3 3.0 0 0.1 3.2 — 200Comparative 3.0 0 0.1 0 108 105 example 1 Comparative 0 0 0.1 3.0 190Over- example 2 develop- ment Comparative 0 1.52 0.1 0.5 Over- Over-example 3 develop- develop- ment ment Comparative 0 1.52 0.1 2.0 100 —example 4

It is apparent from the aforementioned results that thephotopolymerizable resin compositions of Examples 1 and 2 containing allthree photopolymerization initiators (B1), (B2), and (B4) display highersensitivity than those of Comparative Examples 1 and 2 containing twophotoinitiators out of the three and those of Comparative Examples 3 and4 containing benzophenone in place of (B4). There exists an optimalvalue for the amount of (B2) regarding the sensitivity and thesensitivity decreases as the addition increases.

The 10 μm-thick films formed from the photopolymerizable resincompositions of Example 2 and Comparative Examples 1 and 3 were testedby an exposure spectrometer (SS25CP, tradename of Nihon Bunko K.K.) forthe relationship between the wavelength of light for exposure and thesensitivity (curing rate). Concretely, the specimen was exposed to lightof a given wavelength range in steps by changing the exposure time andposition, developed by a 0.7 wt % aqueous solution of diethanolamine at28° C. for 40 seconds, and then examined for the number of steps of theresidual film on the base plate for each wavelength and exposure time.In this case, the greater the number of steps, the higher thesensitivity. The results are shown in Table 2.

TABLE 2 Wavelength (nm) 33 365 405 437 Number of Example 2 5 6 0 0 stepsexample 1 Comparative 4 4 0 0 example 1 Comparative 0 0 0 0 example 3

It is seen from the results shown in Table 2 that the addition of (B 1),(B2), and (B4) enhances the sensitivity in the wavelength range 300-400nm, but curing does not occur in the same wavelength range whenbenzophenone is substituted for (B4).

Next, the 10 μm-thick films formed from the photopolymerizable resincompositions of Example 2 and Comparative Example 1 were tested forresolution. The specimen was exposed to light at 200 mJ/cm² through aline and space mask for resolution measurement (available from NihonFirukon K.K.) and developed by a 0.7 wt % aqueous solution ofdiethanolamine at 28° C. for 40 seconds. The exposed portion remained aslines on the plate without any loss and the unexposed portion came offto form a space between lines after development and, when this happened,the minimum width of the line was taken as resolution. The results areshown in Table 3, in which the numerator designates the width of lineand the denominator the width of space, both in μm.

TABLE 3 Development time (seconds) 40 60 90 120 150 180 Example 2 20/2020/20 30/30 30/30 60/60 60/60 Comparative 20/20 30/30 40/40 60/60 80/80100/100 example 1

Table 3 indicates that the specimen of Example 2 is superior to that ofComparative Example 1 in adhesion of patterns even after a longdevelopment time. This means that the addition of N-phenylglycinepromotes the curing in the inside and causes the patterns to adhere tothe base plate without dissolving during a long development time, thatis, the addition provides a wide latitude in development for stablepatterning.

Furthermore, the 40 μm-thick films formed from the photopolymerizableresin compositions of Example 2 and Comparative Example 1 were observedfor the shape of a line and space pattern. The specimen was exposed tolight at 200 mJ/cm² through the aforementioned line and space mask forresolution measurement and developed by a 1.4 wt % aqueous solution ofdiethanolamine at 28° C. for 100 seconds to give a pattern with a 40μm-wide line and a 40 μm-wide space. The cross section of the patternobtained from the photopolymerizable resin composition of Example 2 isshown in FIG. 1 and that of Comparative Example 1 in FIG. 2.

As is apparent from a comparison of FIGS. 1 and 2, thephotopolymerizable resin composition of Example 2 cures well in theinside and maintains the lines in good shape while that of ComparativeExample 1 give lines which show thinning and are curved on the side.

Examples 4-5 and Comparative Examples 5-6

The resin component (A) was prepared from 25 parts by weight each ofdipentaerythritol hexaacrylate (DPHA, tradename of Nippon Kayaku Co.,Ltd.) and pentaerythritol acrylate (PET-30, tradename of KyoeishaChemical Co., Ltd.) as (A1) and 50 parts by weight of isobornylmethacrylate-methacrylic acid-epoxycyclohexylmethyl methacrylatecopolymer (molar ratio 28/36/36) (Cyclomer M100, tradename of DaicelChemical Industries, Ltd.) as (A2).

To 100 parts by weight of the sum of (A1) and (A2) were added thefollowing compounds respectively in the amounts shown in Table 4 to give4 kinds of colored photopolymerizable resin compositions in homogeneoussolution; Ceroxide 2021P (tradename of Daicel Chemical Industries, Ltd.)for providing heat resistance during heat treatment, a silane couplingagent (S510, tradename of Chisso Corporation) for improving the adhesionto the base plate, a phthalocyanine blue dispersion in a 3:2 mixture byweight of diglyme and propylene glycol monomethyl ether acetate (PGMEA)as blue pigment, and photopolymerization initiator (B) made up of2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (Irgacure907, tradename of Ciba) as (B4), 4,4′-diethylaminobenzophenone (EABF,tradename of Hodogaya Chemical Co., Ltd.) as (B1), and N-phenylglycineas (B2), and a known photopolymerization initiatorbis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (CGI-819, tradename ofCiba) or 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine(TAZ-110, tradename of Midori Kagaku K.K.).

TABLE 4 Amount added (part by weight) Comparative Comparative Example 4Example 5 example 5 example 6 2021P 5.5 5.5 5.5 5.5 S510 1.5 1.5 1.5 1.5Phthalocyanine 28 28 28 28 blue Diglyme 240 240 240 240 PGMEA 160 160160 160 Irgacure 907 2.5 2.5 2.5 2.5 EABF 0.42 2.0 0.42 0.42 CGI-819 2.52.5 2.5 0 N- 0.83 1.5 0 0 Phenylglycine TAZ-110 0 0 0 2.5

Each of the photopolymerizable resin compositions thus obtained wasapplied to a glass base plate by a spin coater to a film thickness afterdrying of 1.5 μm and dried at 60° C. for 5 minutes to form a film forcolor filter and the film was tested for the sensitivity andchromaticity under the following conditions. The results are shown inTable 5.

[Determination of Sensitivity]

With the use of a wedge filter for sensitivity measurement, the specimenwas exposed to ultraviolet light with i-line as standard at 100 mJ/cm²and then developed by 0.01N aqueous potassium hydroxide at 25° C. for 30seconds as described above and the minimum exposure giving a residualfilm after development was taken as sensitivity.

[Determination of Chromaticity]

The aforementioned film for color filter on the glass base plate wasexposed to ultraviolet light with i-line as standard at 300 mJ/cm² anddeveloped by 0.01N aqueous potassium hydroxide at 25° C. for 30 secondsto give a blue pattern, which was postbaked at 200° C. for 30 minutesand tested for the chromaticity with the aid of a color analyzer(TC-1800MK2, tradename of Tokyo Denshoku K.K.).

TABLE 5 Comparative Comparative Example 4 Example 5 example 5 example 6Sensitivity 50 35 65 35 (mj/cm²) Hue x 0.145 0.145 0.145 0.145 Hue y0.155 0.155 0.155 0.155 Lightness Y 21 20.6 21 19.5

The results in Table 5 indicate that the specimen of Example 4 is moresensitive than that of Comparative Example 5. Moreover, the blue filterof Example 5 shows higher lightness (Y) than that of Comparative Example6 at the same hue (x, y) and the effect for enhancing the sensitivitywas produced without greatly influencing the color characteristics andthus the polymerizable resin compositions tested were confirmed to behighly transparent and show good reproducibility of the pigment color.

Examples 6-11 and Comparative Examples 7-9

The resin component (A) was prepared from 50 parts by weight of amixture of dipentaerythritol hexaacrylate and dipentaerythritolpentaacrylate (KAYARAD-DPHA, tradename of Nippon Kayaku Co., Ltd.) as(A1) and 88.5 parts by weight of a 56.5% propylene glycol monomethylether acetate solution (50 parts by weight as solid) offluorenebisphenol type epoxy acrylate-acid anhydride additionalternating copolymer (V-301M, tradename of Nippon Steel Chemical Co.,Ltd.) as (A2).

To 100 parts by weight of the sum of (A1) and (A2) as solid were added15.7 parts by weight of YX4000H (tetramethylbiphenyl type epoxy resinavailable from Yuka Shell Epoxy K.K.) as thermal crosslinking agent, thephotopolymrization initiators shown in Tables 6 and 7, 0.23 part byweight of surfactant FC430 (available from Sumitomo 3M Ltd.), and 540parts by weight of propylene glycol monomethyl ether acetate as solventto give a homogeneous solution. The solution was then mixedhomogeneously with 318 parts by weight of a phthalocyanine blue (PB15:6)dispersion (available from Mikuni Color Works Ltd., content of pigment20%, with propylene glycol monomethyl ether acetate used as dispersionmedium). In this manner, 9 kinds of colored photopolymerizable resincompositions, that is, blue inks, were prepared in which the weightratio of pigment to resin was 0.55.

Each of the colored photopolymerizable resin compositions was applied bya spin coater to a glass base plate to a film thickness after drying of1.1 μm and dried at 80° C. for 5 minutes to form a film for color filteron the glass base plate. The film was further treated as in Example 4and tested for the sensitivity and chromaticity, except carrying out thedevelopment by a 0.4% aqueous solution of sodium carbonate at 25° C. for40 seconds. In addition, spectral exposure was conducted on the films asin Example 2 to determine the sensitivity at each wavelength. Theresults of Examples 6-10 are shown in Table 6 and those of Example 11and Comparative Examples 7-9 in Table 7. The photopolymerizationinitiators listed in Tables 6 and 7 are designated in the same manner asin Example 4 and Table 4 and those newly appearing here aretetra(t-butylperoxycarbonyl)benzophenone (BTTB available from NOF Corp.,25% toluene solution, the numerical value given in Tables 6 and 7designating solid in part by weight) and Triazine PP (available fromNihon Siber Hegner K.K.).

TABLE 6 Amount added (part by weight) Exam- Example 6 Example 7 Example8 Example 9 ple 10 Triazine PP 0 0 0.5 0.5 0 Irgacure 907 3 3 3 0 0 EABF2 2 2 2 2 CGI-819 2.5 0 0 0 2.5 N- 2 1.5 1.5 1.5 2 Phenylglycine BTTB 11 1 1 1 Sensitivity 35 53 35 75 80 (mj/cm²) Chromaticity Hue x 0.1410.141 0.141 0.141 0.141 Hue y 0.154 0.154 0.154 0.154 0.154 Lightness Y21.1 21.1 21 20.9 21.1 Number of steps Wavelength (nm) 365 6 6 6 6 6 4057 7 7 7 7 437 4 4 4 4 4

TABLE 7 Amount added (part by weight) Comparative Comparative ExampleComparative example 7 example 8 11 example 9 Triazine PP 0 0 0 3Irgacure 907 3 3 0 3 EABF 0 2 2 1 CGI-819 2.5 2.5 0 0 N-Phenylglycine 20 2 0 BTTB 1 1 1 0 Sensitivity Flatting out Flatting out 100 35 (mj/cm²)in in Roughen- development development ing of surface Chromaticity Hue x— — 0.141 0.14 Hue y — — 0.154 0.154 Lightness Y — — 20.8 19.4 Number ofsteps Wavelength (nm) 365 6 6 6 6 405 2 7 7 7 437 0 0 4 4

In Examples 6 to 10, the copresence of three photopolymerizationinitiators (B1), (B2), and (B3), namely, diethylaminobenzophenone,N-phenylglycine, and BTTB with 0.5% or less of an i-line-sensitivephotoinitiator or a triazine-based photoinitiator helped to give blueinks of high sensitivity, which in turn gave color filters of excellentlightness. On the other hand, in Comparative Example 9, the use of noneof (B2) and a relatively large amount of Triazine PP resulted in an inkof high sensitivity, yet a blue filter of inferior lightness. InComparative Examples 7 and 8, the absence of diethylaminobenzophenone(B1) or N-phenylglycine (B2) resulted in reduced sensitivity and led toflatting out during development. A comparison of spectral exposure inthe examples and comparative examples suggests that the sensitivity isenhanced in the copresence of diethylaminobenzophenone, N-phenylglycine,and BTTB as curing occurs even at the g-line (437 nm) in theircopresence. Moreover, the results of Example 11 suggest that theaddition of a curing agent sensitive to the i-line is desirable foreffecting surface curing.

INDUSTRIAL APPLICABILITY

Polymerizable resin compositions of this invention excel in resolution,adhesion of patterns, development latitude, and curing on the surfaceand inside, exhibit high sensitivity to ultraviolet light in thewavelength range 300-450 nm, and are transparent with good colorreproducibility when mixed with colorants. The compositions curesatisfactorily even when the film thickness during light exposure is 10μm or more. As the base of colored photopolymerizable resincompositions, the photopolymerizable resin compositions are highlytransparent and give good color reproducibility without significantlyinfluencing the color characteristics.

On account of these properties, polymerizable resin compositions of thisinvention can be used advantageously in insulating films, insulatingfilms for semiconductors, protective films for color filters, inks forcolor filters, colored films, resist materials, resists forsemiconductors, and insulating spacers for touch panels and alsoincorporated into liquid crystal color displays, liquid crystal colortelevision, and color image sensors.

What is claimed is:
 1. A photopolymerizable resin composition containingcomponent (A) composed of a resin and/or a resin-forming ingredient anda photopolymerization initiator (B) wherein the component (A) comprisesan addition polymerizable compound (A1) showing a boiling point of 100°C. or higher at normal pressure and having at least 2 ethylenicallyunsaturated groups in the molecule and the photopolymerization initiator(B) comprises a diaminobenzophenone compound (B1) represented by thefollowing general formula (1)

in which R is a hydrogen atom or an alkyl group with 1-3 carbon atomsand R's are identical with or different from each other, anN-phenylglycine compound (B2) represented by the following generalformula (2)

in which R is an alkyl group with 1-8 carbon atoms, R′ is a hydrogenatom or an alkyl group with 1-8 carbon atoms, n is an integer in therange 0-5, and R's are identical with or different from each other whenn is 2 or more, and at least one kind of compound selected from a groupof a 3,3′,4,4′-tetra(alkylperoxycarbonyl)benzophenone (B3) representedby the following general formula (3)

in which R is an alkyl group with 1-8 carbon atoms and R's are identicalwith or different from each other,2-methyl-1-[4-(thiomethyl)phenyl]-2-morpholinopropan-1-one (B4), and a1,3,5-triazine derivative (B5) containing at least one trihalomethylgroup as substituent; wherein said composition comprises 100 parts byweight of the component (A) composed of the resin and/or theresin-forming ingredient, 0.05-2.0 parts by weight of thediaminobenzophenone compound (B1), 0.2-2 parts by weight of theN-phenylglycine compound (B2), 0.1-2.5 parts by weight of the3,3′,4,4′-tetra(alkylperoxycarbonyl)benzophenone (B3), 0-5 parts byweight of the 2-methyl-1-[4-(thiomethyl)phenyl]-2-morpholinopropan-1-one(B4), and 0-1 part by weight of the 1,3,5-triazine derivative (B5).
 2. Aphotopolymerizable resin composition as described in claim 1 wherein thecomponent (A) composed of a resin and/or a resin-forming ingredientcomprises the addition-polymerizable compound (A1) and an alkali-solubleresin (A2) and the ratio (A1)/(A2) by weight is 10/90-90/10.
 3. Aphotopolymerizable resin composition as described in claim 1, whereinsaid composition comprises 100 parts by weight of the component (A)composed of the resin and/or the resin-forming ingredient, 0.05-2.0parts by weight of the diaminobenzophenone compound (B1), 0.2-2 parts byweight of the N-phenylglycine compound (B2), 0.1-2.5 parts by weight ofthe 3,3′,4,4′-tetra(alkylperoxycarbonyl)benzophenone (B3), 1-5 parts byweight of the 2-methyl-1-[4-(thiomethyl)phenyl]-2-morpholinopropan-1-one(B4), and 0-0.5 part by weight of the 1,3,5-triazine derivative (B5). 4.A photopolymerizable resin composition as described in claim 1, whereinthe resin component (A) composed of the resin and/or the resin-formingingredient comprises the addition-polymerizable compound (A1) and thealkali-soluble resin (A2) at the ratio (A1)/A2) by weight in the range10/90-90/10 and said composition comprises 100 parts by weight of thesum of (A1) and (A2), 0.05-2.0 parts by weight of thediaminobenzophenone compound (B1), 0.2-2 parts by weight of theN-phenylglycine compound (B2), 0.1-2.5 parts by weight of the3,3′,4,4′-tetra(alkylperoxycarbonyl)benzophenone (B3), 1-5 parts byweight of the 2-methyl-1-[4-(thiomethyl)phenyl]-2-morpholinopropan-1-one(B4), and 0-0.5 part by weight of the 1,3,5-triazine derivative (B5). 5.A film obtained by applying the photopolymerizable resin compositiondescribed in claim 1 followed by curing.
 6. A photopolymerizable resincomposition containing component (A) composed of a resin and/or aresin-forming ingredient and a photopolymerization initiator (B) whereinthe component (A) comprises an addition polymerizable compound (A1)showing a boiling point of 100° C. or higher at normal pressure andhaving at least 2 ethylenically unsaturated groups in the molecule andthe photopolymerization initiator (B) comprises a diaminobenzophenonecompound (B1) represented by the following general formula (1)

in which R is a hydrogen atom or an alkyl group with 1-3 carbon atomsand R's are identical with or different from each other, anN-phenylglycine compound (B2) represented by the following generalformula (2)

in which R is an alkyl group with 1-8 carbon atoms, R′ is a hydrogenatom or an alkyl group with 1-8 carbon atoms, n is an integer in therange 0-5, and R's are identical with or different from each other whenn is 2 or more, and at least one kind of compound selected from a groupof a 3,3′,4,4′-tetra(alkylperoxycarbonyl)benzophenone (B3) representedby the following general formula (3)

in which R is an alkyl group with 1-8 carbon atoms and R's are identicalwith or different from each other,2-methyl-1-[4-(thiomethyl)phenyl]-2-morpholinopropan-1-one (B4), and a1,3,5-triazine derivative (B5) containing at least one trihalomethylgroup as substituent, wherein a blue colorant is incorporated.
 7. A blueink comprising the photopolymerizable resin composition described inclaim
 6. 8. A film obtained by applying the blue ink described in claim7 followed by curing.
 9. A color filter comprising the film described inclaim 5 or 8.